Literature DB >> 22065239

Ethyl 2-[2-(3-meth-oxy-phen-yl)hydrazinyl-idene]-3-oxobutano-ate.

Hoong-Kun Fun, Safra Izuani Jama Asik, Ibrahim Abdul Razak, Shobhitha Shetty, Balakrishna Kalluraya.

Abstract

The title compound, C(13)H(16)N(2)O(4), is approximately planar (r.m.s. deviation = 0.065 Å for the 19 non-H atoms). An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif and the mol-ecule adopts an E conformation with respect to the central C=N double bond. In the crystal, pairs of inter-molecular C-H⋯O hydrogen bonds link adjacent mol-ecules into inversion dimers. The crystal structure also features weak C-H⋯π inter-actions.

Entities: Chemical Disease Species

Year: 2011 PMID： 22065239 PMCID： PMC3201266 DOI： 10.1107/S1600536811039444

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the biological activity of oxobutanoate derivatives, see: Billington et al. (1979 ▶); Stancho et al. (2008 ▶); For the biological activity of pyrazole derivatives, see: Rai et al. (2008 ▶); Girisha et al. (2010 ▶); Isloor et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For a related structure, see: Fun et al. (2011 ▶).

Experimental

Crystal data

C13H16N2O4 M = 264.28 Triclinic, a = 5.7796 (4) Å b = 7.4691 (5) Å c = 16.9842 (11) Å α = 77.956 (2)° β = 89.394 (2)° γ = 72.547 (2)° V = 682.97 (8) Å3 Z = 2 Mo Kα radiation μ = 0.10 mm−1 T = 296 K 0.53 × 0.36 × 0.25 mm

Data collection

Bruker APEX DUO CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.942, T max = 0.977 11969 measured reflections 3108 independent reflections 2419 reflections with I > 2σ(I) R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.050 wR(F 2) = 0.180 S = 1.04 3108 reflections 179 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.22 e Å−3 Δρmin = −0.20 e Å−3 Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶). Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811039444/hb6413sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811039444/hb6413Isup2.hkl Supplementary material file. DOI: 10.1107/S1600536811039444/hb6413Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₃H₁₆N₂O₄	Z = 2
M_r = 264.28	F(000) = 280
Triclinic, P1	D_x = 1.285 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7796 (4) Å	Cell parameters from 5306 reflections
b = 7.4691 (5) Å	θ = 2.9–31.0°
c = 16.9842 (11) Å	µ = 0.10 mm⁻¹
α = 77.956 (2)°	T = 296 K
β = 89.394 (2)°	Block, yellow
γ = 72.547 (2)°	0.53 × 0.36 × 0.25 mm
V = 682.97 (8) Å³

Bruker APEX DUO CCD diffractometer	3108 independent reflections
Radiation source: fine-focus sealed tube	2419 reflections with I > 2σ(I)
graphite	R_int = 0.021
φ and ω scans	θ_max = 27.5°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
T_min = 0.942, T_max = 0.977	k = −9→9
11969 measured reflections	l = −22→22

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.1108P)² + 0.0852P] where P = (F_o² + 2F_c²)/3
3108 reflections	(Δ/σ)_max < 0.001
179 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	U_iso*/U_eq
O1	0.1556 (2)	0.3160 (2)	0.33318 (7)	0.0707 (4)
O2	1.1429 (2)	−0.1952 (2)	0.34750 (7)	0.0743 (4)
O3	0.2371 (2)	0.53420 (17)	0.05938 (7)	0.0633 (3)
O4	−0.1755 (2)	0.5181 (2)	0.26261 (8)	0.0777 (4)
N1	0.5632 (2)	0.27108 (17)	0.15513 (8)	0.0466 (3)
N2	0.4082 (2)	0.29646 (16)	0.21110 (7)	0.0465 (3)
C1	0.8606 (3)	0.0293 (2)	0.25233 (9)	0.0506 (4)
H1A	0.7505	0.0426	0.2927	0.061*
C2	1.0931 (3)	−0.0981 (2)	0.26917 (9)	0.0522 (4)
C3	1.2578 (3)	−0.1225 (2)	0.20927 (10)	0.0542 (4)
H3A	1.4129	−0.2093	0.2208	0.065*
C4	1.1857 (3)	−0.0148 (2)	0.13213 (9)	0.0553 (4)
H4A	1.2943	−0.0305	0.0915	0.066*
C5	0.9560 (3)	0.1162 (2)	0.11373 (9)	0.0505 (3)
H5A	0.9107	0.1890	0.0617	0.061*
C6	0.7950 (2)	0.13607 (19)	0.17489 (8)	0.0441 (3)
C7	0.1888 (2)	0.41968 (19)	0.19492 (8)	0.0461 (3)
C8	0.0353 (3)	0.4262 (2)	0.26510 (9)	0.0528 (4)
C9	0.0175 (4)	0.3139 (4)	0.40468 (11)	0.0865 (7)
H9A	−0.1166	0.2641	0.3986	0.104*
H9B	−0.0475	0.4429	0.4141	0.104*
C10	0.1857 (5)	0.1891 (5)	0.47226 (13)	0.1126 (10)
H10A	0.0990	0.1788	0.5207	0.169*
H10B	0.3132	0.2433	0.4792	0.169*
H10C	0.2545	0.0638	0.4609	0.169*
C11	0.0984 (3)	0.5402 (2)	0.11476 (9)	0.0487 (3)
C12	−0.1580 (3)	0.6703 (2)	0.09875 (10)	0.0597 (4)
H12A	−0.1847	0.7315	0.0426	0.090*
H12B	−0.1853	0.7663	0.1305	0.090*
H12C	−0.2683	0.5963	0.1129	0.090*
C13	1.3843 (3)	−0.3131 (4)	0.37051 (12)	0.0847 (6)
H13A	1.3949	−0.3739	0.4266	0.127*
H13B	1.4920	−0.2357	0.3616	0.127*
H13C	1.4297	−0.4096	0.3389	0.127*
H1N1	0.517 (3)	0.341 (3)	0.1067 (12)	0.065 (5)*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0532 (7)	0.0947 (9)	0.0492 (6)	−0.0042 (6)	0.0115 (5)	−0.0101 (6)
O2	0.0537 (7)	0.0919 (9)	0.0512 (6)	0.0048 (6)	0.0072 (5)	0.0013 (6)
O3	0.0516 (6)	0.0726 (7)	0.0522 (6)	−0.0059 (5)	0.0090 (5)	−0.0036 (5)
O4	0.0511 (7)	0.0915 (9)	0.0686 (8)	0.0058 (6)	0.0189 (5)	−0.0105 (6)
N1	0.0392 (6)	0.0488 (6)	0.0478 (6)	−0.0087 (5)	0.0078 (5)	−0.0093 (5)
N2	0.0400 (6)	0.0487 (6)	0.0508 (6)	−0.0117 (5)	0.0082 (5)	−0.0138 (5)
C1	0.0434 (7)	0.0565 (8)	0.0474 (7)	−0.0094 (6)	0.0133 (6)	−0.0106 (6)
C2	0.0459 (8)	0.0560 (8)	0.0482 (8)	−0.0087 (6)	0.0081 (6)	−0.0073 (6)
C3	0.0406 (7)	0.0566 (8)	0.0602 (9)	−0.0061 (6)	0.0114 (6)	−0.0142 (6)
C4	0.0468 (8)	0.0621 (9)	0.0554 (8)	−0.0128 (6)	0.0190 (6)	−0.0158 (6)
C5	0.0471 (8)	0.0526 (8)	0.0486 (7)	−0.0124 (6)	0.0115 (6)	−0.0086 (6)
C6	0.0394 (7)	0.0429 (6)	0.0492 (7)	−0.0108 (5)	0.0080 (5)	−0.0112 (5)
C7	0.0409 (7)	0.0474 (7)	0.0493 (7)	−0.0105 (5)	0.0078 (5)	−0.0134 (6)
C8	0.0458 (7)	0.0558 (8)	0.0533 (8)	−0.0087 (6)	0.0088 (6)	−0.0145 (6)
C9	0.0712 (12)	0.1166 (17)	0.0559 (10)	−0.0087 (11)	0.0213 (9)	−0.0142 (10)
C10	0.1045 (18)	0.146 (2)	0.0604 (13)	−0.0132 (17)	0.0132 (12)	−0.0019 (14)
C11	0.0444 (7)	0.0495 (7)	0.0518 (8)	−0.0124 (6)	0.0054 (6)	−0.0127 (6)
C12	0.0452 (8)	0.0624 (9)	0.0617 (9)	−0.0073 (6)	0.0031 (6)	−0.0054 (7)
C13	0.0576 (10)	0.1074 (16)	0.0643 (11)	0.0002 (10)	−0.0048 (8)	−0.0013 (10)

O1—C8	1.3321 (19)	C5—C6	1.3885 (19)
O1—C9	1.446 (2)	C5—H5A	0.9300
O2—C2	1.3635 (19)	C7—C11	1.469 (2)
O2—C13	1.416 (2)	C7—C8	1.479 (2)
O3—C11	1.2286 (18)	C9—C10	1.471 (3)
O4—C8	1.2018 (18)	C9—H9A	0.9700
N1—N2	1.3029 (16)	C9—H9B	0.9700
N1—C6	1.4077 (17)	C10—H10A	0.9600
N1—H1N1	0.871 (19)	C10—H10B	0.9600
N2—C7	1.3159 (17)	C10—H10C	0.9600
C1—C6	1.379 (2)	C11—C12	1.500 (2)
C1—C2	1.386 (2)	C12—H12A	0.9600
C1—H1A	0.9300	C12—H12B	0.9600
C2—C3	1.388 (2)	C12—H12C	0.9600
C3—C4	1.381 (2)	C13—H13A	0.9600
C3—H3A	0.9300	C13—H13B	0.9600
C4—C5	1.385 (2)	C13—H13C	0.9600
C4—H4A	0.9300

C8—O1—C9	115.96 (13)	O1—C8—C7	112.55 (12)
C2—O2—C13	117.72 (13)	O1—C9—C10	106.80 (17)
N2—N1—C6	119.45 (12)	O1—C9—H9A	110.4
N2—N1—H1N1	117.5 (13)	C10—C9—H9A	110.4
C6—N1—H1N1	123.0 (13)	O1—C9—H9B	110.4
N1—N2—C7	121.32 (12)	C10—C9—H9B	110.4
C6—C1—C2	118.99 (12)	H9A—C9—H9B	108.6
C6—C1—H1A	120.5	C9—C10—H10A	109.5
C2—C1—H1A	120.5	C9—C10—H10B	109.5
O2—C2—C1	114.90 (12)	H10A—C10—H10B	109.5
O2—C2—C3	123.92 (13)	C9—C10—H10C	109.5
C1—C2—C3	121.17 (13)	H10A—C10—H10C	109.5
C4—C3—C2	118.42 (13)	H10B—C10—H10C	109.5
C4—C3—H3A	120.8	O3—C11—C7	118.97 (13)
C2—C3—H3A	120.8	O3—C11—C12	119.17 (13)
C3—C4—C5	121.74 (13)	C7—C11—C12	121.85 (13)
C3—C4—H4A	119.1	C11—C12—H12A	109.5
C5—C4—H4A	119.1	C11—C12—H12B	109.5
C4—C5—C6	118.40 (13)	H12A—C12—H12B	109.5
C4—C5—H5A	120.8	C11—C12—H12C	109.5
C6—C5—H5A	120.8	H12A—C12—H12C	109.5
C1—C6—C5	121.26 (13)	H12B—C12—H12C	109.5
C1—C6—N1	121.21 (12)	O2—C13—H13A	109.5
C5—C6—N1	117.53 (12)	O2—C13—H13B	109.5
N2—C7—C11	124.15 (12)	H13A—C13—H13B	109.5
N2—C7—C8	114.01 (12)	O2—C13—H13C	109.5
C11—C7—C8	121.84 (12)	H13A—C13—H13C	109.5
O4—C8—O1	122.46 (14)	H13B—C13—H13C	109.5
O4—C8—C7	124.99 (14)

C6—N1—N2—C7	−179.23 (12)	N2—N1—C6—C5	−178.85 (12)
C13—O2—C2—C1	−173.78 (16)	N1—N2—C7—C11	−0.8 (2)
C13—O2—C2—C3	6.6 (3)	N1—N2—C7—C8	178.50 (12)
C6—C1—C2—O2	179.03 (14)	C9—O1—C8—O4	−0.3 (3)
C6—C1—C2—C3	−1.3 (2)	C9—O1—C8—C7	−179.75 (16)
O2—C2—C3—C4	−179.68 (15)	N2—C7—C8—O4	−174.52 (16)
C1—C2—C3—C4	0.7 (2)	C11—C7—C8—O4	4.8 (3)
C2—C3—C4—C5	0.4 (2)	N2—C7—C8—O1	4.92 (19)
C3—C4—C5—C6	−0.9 (2)	C11—C7—C8—O1	−175.78 (13)
C2—C1—C6—C5	0.9 (2)	C8—O1—C9—C10	−178.4 (2)
C2—C1—C6—N1	−178.33 (12)	N2—C7—C11—O3	−3.6 (2)
C4—C5—C6—C1	0.2 (2)	C8—C7—C11—O3	177.20 (13)
C4—C5—C6—N1	179.44 (13)	N2—C7—C11—C12	176.54 (13)
N2—N1—C6—C1	0.4 (2)	C8—C7—C11—C12	−2.7 (2)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3	0.87 (2)	1.87 (2)	2.5629 (18)	135.3 (18)
C5—H5A···O3ⁱ	0.93	2.54	3.4389 (19)	164
C13—H13C···O4ⁱⁱ	0.96	2.58	3.219 (3)	124
C12—H12B···Cg1ⁱⁱⁱ	0.96	2.82	3.6422 (17)	145

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3	0.87 (2)	1.87 (2)	2.5629 (18)	135.3 (18)
C5—H5A⋯O3ⁱ	0.93	2.54	3.4389 (19)	164
C13—H13C⋯O4ⁱⁱ	0.96	2.58	3.219 (3)	124
C12—H12B⋯Cg1ⁱⁱⁱ	0.96	2.82	3.6422 (17)	145

Symmetry codes: (i) ; (ii) ; (iii) .

8 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Regioselective reaction: synthesis, characterization and pharmacological studies of some new Mannich bases derived from 1,2,4-triazoles.

Authors: Arun M Isloor; Balakrishna Kalluraya; Prashanth Shetty
Journal: Eur J Med Chem Date: 2009-05-05 Impact factor: 6.514

3. Synthesis and pharmacological study of 1-acetyl/propyl-3-aryl-5-(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)-2-pyrazoline.

Authors: K S Girisha; Balakrishna Kalluraya; Vijaya Narayana
Journal: Eur J Med Chem Date: 2010-07-24 Impact factor: 6.514

4. Convenient access to 1,3,4-trisubstituted pyrazoles carrying 5-nitrothiophene moiety via 1,3-dipolar cycloaddition of sydnones with acetylenic ketones and their antimicrobial evaluation.

Authors: N Satheesha Rai; Balakrishna Kalluraya; B Lingappa; Shaliny Shenoy; Vedavati G Puranic
Journal: Eur J Med Chem Date: 2007-08-30 Impact factor: 6.514

5. Biosynthesis of ethylene from methionine. Isolation of the putative intermediate 4-methylthio-2-oxobutanoate from culture fluids of bacteria and fungi.

Authors: D C Billington; B T Golding; S B Primrose
Journal: Biochem J Date: 1979-09-15 Impact factor: 3.857